Mixed esters



organic acids and a polyhydric alcohol.

MIXED ESTERS Sylvan Owen Greenlee, Racine, Wis., assignor to S. C.Johnson & Son, Inc., Racine, Wis.

No Drawing. Application April 11, 1955 Serial No. 500,696

22 Claims. (Cl. 260-19) This invention relates to mixed esters of two ormore More particularly, this invention relates to new synthetic estersprepared from a polyhydric alcohol and a mixture of acids comprising oneor more unsaturated monocarboxylic acids pounded with one or morematerials which contribute the plastici'zing and/ or dryingcharacteristics. Since the resin and plasticizefor drying oil must becompletely miscible with one another, certain other properties of theresin are sacrificed." For example, a formulator. will choose a verysoluble resin because of its miscibility: even though 'the product isinferiorwith respect to toughness, chemical resistance or flexibility. ol

Important resin plasticizers are the drying oils, which United State PtfitO T 2,907,724 Patented Oct. 6,? 1959 Due to the fact that theexemplified polyhydric alcohol is trihydric, it is obvious that amaximum of 3 mols of acids may be used. In prior applications, SerialNos. 464,607 and 489,300, filed October 25, 1954, and February 18, 1955,respectively, there are disclosed a number .of compounds which aresuitable for use as the aryl-sub stituted pentanoic acid hereincontemplated. These ma terials, which are referred to for convenience asDiphenolic Acids, consist of thecondensation products of levucontain theglycerides of unsaturated acids of 18 to 22 A carbon atoms, and thesimpler esters of such acids. These oils are highly desirable not onlyfor plasticizing, butalso for the conversion characteristics which they-impart due to their unsatunation. The present compositions provide ameans of chemically in each molecule are the mixed esters prepared fromone or more unsaturated acids; polyhydric. alcohol, and anaryl-substituted pentanoic acid. Such compositions may be prepared, forexample, by reacting 1 mol of a Diphenolic Acid, such compositionproduct of castor oil acids.

linic acid and phenol, substituted phenols, or mixtures thereof. It isto be understood that the phenolic nuclei of the Diphenolic Acid may besubstituted with any groups which will not interfere with theesterification re actions. For example, the nuclei may be alkylated withalkyl groups of from 1-5 carbon atoms as disclosed ,in .Serial No.489,300 or they may be halogenated. The long-chain unsaturatedmonocarboxylic acids suitable for use in preparing the mixed esters ofthis invention include those containing at least about 10 carbon atoms.Illustrative of such acids are the drying oil fatty acids .whichnormally contain from 18 to 2-2 carbon atoms such as'acids obtained bythe saponification of naturallyoecurring unsaturated vegetable oilsincluding China -wood oi-l, oiti eica oil, linseed oil, soybean oil,corn oil, and cottonseed oil. The fish oils constitute another importantsource of operableunsaturated acids. These ma .terials, derivedprincipally from the menhaden and the sardine, contain: the glyceridesof highly unsaturated acids and have an iodine value ranging from about130 to 190. Suitable acids may be produced by another synthetic means,for example, mixed linoleic acids may be obtained bysaponifying'dehydrated castor oil. Oleic acid may. be 'used toprepare alinoleic acid by hydroxylating the same --to-formgdihydroxystearic acid,followed by dehydration of the latter. Lower molecular weightunsaturated acids mayalso be used if only air-drying characteristicszaredesired, butthose containing less than about 10 carbon atoms .contributelittle plasticization. An example. of one of the lower plasticizingacids contemplated is an decenoic acid, acommercially availablematerial, the de- The polyhydric alcohols used iiithe preparation of'thesubject mixed esters may be of the nonresinous type and also of theresinous type. Illustrating the nonresinous type of polyhydric. alcoholsare ethylene glycol, polyethyleneglycols, propyleneglycol, polypropyleneglycols,

of linoleic acidand 1 mol of-glycerol.

-1,4-butane-diol, 2,5-pentane-diol, 1,6-hexane-diol, neo pentyl glycol,glycerol, erythritol, pentaerythritol, polypentaerythritols, .sorbitol,mannitol, alpha-methyl gluf coside, polyallyl glycols, diethanolamine,triethanolamine, and tetramethylol cyclohexanol. j

Illustrating the resinous polyhydric alcohols which may onenses cneegcneememu.o0.0m

' chlorohydrins.

. 3 be usedtin the-preparation-of the subject mixed esters are thereaction products of di-and trihydric phenols with For example, thereaction of bis(4-hydroxyphenyl) isopropylidene with ethylenechlorohydrin orglycerol monochlorohydr-irr yields a resinous polyhydricalcohol. The reaction of the'same-dihydric phenol with cpichlorohydrinor glycerol dichlorohydrin produces resinous polyhydric alcohols whichin some cases contain epoxide groups -in addition to the alcoholic*hydroxyl groups. (The epoxide-containingproducts-are well-illus'trated'by the commercially avaliable -Epon resins.) The preparation oftheseresinous polyhydric alcohols arc described in U. 8. Patents2,456,408, 2,503,726, 2,615,008, 2,668, 805, and2,668,807.

Other'typesof'resinous polyhydric alcohols are-those prepared by thereactionof phenol-formaldehyde -condensates with-chlorohydrins. An alkylphenol may be condensed with formaldehyde, followed by treatment of analkaline solution of this intermediate methycl deriva tive with achlorohydrin such as glycerol monochlorohydrinto form aresinouspolyhydric alcohol.

The amount of acids employed to: preparethe subject compositionsdepends-upon the particularpolyhydric al- 'coholchosen. It is obviousthat to prepare a-mixed ester, the maximum number of mols of acidsreacted can be no greater than the numberof hydroxyl; groups in thealcohol. The ratio of *Diphenolic Acid to unsaturated acid may bewidely-varied and'is limited only by thedesiredquantum of-influence ofeach material.

"The mixed esters of this invention are conveniently prepared Jbydirectheating'at temperatures of from 190- 275" :C. .with provision for thecontinuous removalof .water produced by the condensation. Since theDiphenolic Acid,:the long-chain unsaturated acids, and the polyhydricalcohols have boiling points which are in all cases above 190 C., .watermay be'removedby-permitting it .to volatilize during esterification.Removal of the .water may also be facilitatedby. continuously bubblingthrough thereaction mixture, during esterification, a stream of inertgas .such as carbon dioxide ornitrogen. It is also sometimes. convenientto facilitate thewaterremoval .by carrying out :thereaction in a vesselprovided withsalcondenser attached thereto through a water trap, addinga sufiicient amountof a .volatile water-insoluble solvent to give refluxat the esterification temperature, continually removingthewater byazeotropicdistillation permitting the solvent to return to thereactionmixture aftenhaving droppedthewater inthe water trap.

The order of addition of the various ingredients, Di-

phenolic Acid, long-chain unsaturated acids, and poly hydricalcohols,,to eachfothermay be varied. Itis some times advantageous tovary the orderof reaction toobtain optimum .results .with aparticularcombination of ingredients ,used. In .the .art .of hightemperature esterification, it is desirable to .usecertainesterificationcatalysts, and-these may housed in the preparationof thesubject coating compositions. Other methods of esterification, such asesterification of polyhydric alcohols with the acid chlorides, or acidinterchange of the high molecular weight acids with materials such asthe acetates of the polyhydric alcohols may be used.

The present mixed esters are polyhydric phenols containing within thesame molecule unsaturated residues of the plasticizing type. Thepolyhydric phenol portion is one which is very reactive with certainmaterials to form compositions which are highly sensitive 5110polymeriza tion to infusible, insoluble coating or molding products.Bis(4-hydroxyphenyl) isopropylidene, also known :as bisphenol, is verysimilar to the dihydric phenol structure introduced into the subjectmixed esters. When reacted with either aldehydes or epoxides, thismaterial yields compositions which are almost quantitatively insolublein drying oils and the simpler esters of unsaturated acids of 18 to 22.carbonatoms. The-presentcornpositions, containing the bisphenol typestructure chemian excellent protective coating material.

cally bound as an integral part of a molecule which also containsthe'plasticizer, maybe reacted with such reagents as aldehydes andepoxides to form compositions which may be polymerized to form valuableinsoluble, infusible compositions. However, in the latter products, theresinous and plasticizing materials are chemically united so that therecanbeqnoiphysical separation thereof during processing, and thecharacteristics contributed by each will be found undiminished in theend product.

Having described the invention,a seriesof illustrative examples arepresented below. ,Theseembodiments are not intended to limit theinvention and should not be so construed. Quantitiesof materialsexpressed are parts by weight unless otherwise indicated.

Example I A monolinseed acid ester of glycerol (a monoglyceride) mixture,heated with continuous agitation to 210 .C. and held at thistemperature until the acid value below 10. The term :acid value asusedthroughout this description .isdefined as the number of :milligramsvof KOH which is equivalent to the acid content of one gramof thesample. The product was ,a uniformlyclear, tacky,.solid,material.

Similarly, .1 ;rnol of linseed-oil was alcoholized with /2 mol ofglycerol to give a glyceride containing 1,.free hydroxyl group and 2linseed acid ester groups. One mol ofithis diglyceride was treated with1 mol'of the same Diphenolic Acid to give a mixed ester from .l molof;the diphenolic acid and 2 mols of linseed acids.

Both of these products, on reaction with formaldehyde, give compositionswhich when spread in thin .protective coating ,films andheat treated for;30.minutes at 150 C. are hard, tough, and tack-free.

zfromphenol land levulinic acid and 1 mol of-linseed oil :fatty acids ina S-neck flask provided witha thermometer,

a mechanical agitator, and reflux condenser attached through a .watertrap was gradually heated r0230" "C.

-withjcontinuous agitation. To'the molten mixture-was added 1.2 mols ofpentaerythritol, after which a small amount.of xylene necessary togivereflux .at'theesterification temperaturewas added. The continuouslyagitated mixture was heated .at 215-225 C. for 6 hours after which .thetemperature was raised to 260 C. and held "at :this temperature for 30minutes, during which time :a waterleg vacuum-of about :30 mm. pressurewas applied to remove thelastztraces of xylene. This-product had an acidvalue of 5.2 and a softening point of 72- 75 C. (Durrans Mercury Method,Journal of Oil and Color Chemical Association, 12, 173-5 [1929].)

This mixed ester was reacted with formaldehydezto give To .parts of themixed ester and 40 parts of xylene was added 24.3 parts ofpara-formaldehyde with .71 part ofoxalic acid as catalyst and theresulting mixture heated with agitation at 104 C. for approximately '1hour. Ninety parts of this product was dissolved in a solvent composedof equal parts of butanol, butyl acetate, and methyl isobutyl ketone togive a nonvolatile content of 35% and a viscosity of A-3 (Gardner BubbleTube Viscosimeter). A thin film of this coating flowed on to a steelpanel and baked for 15 minutes at 200 C. gave a completely tack-freecoating. This thin film exhibited flexibility as shown by ribboningunder a knife edge. This film withstoodiboiling water for 2 hours,diethyl ether for 1 hour, and 10% ammonium hydroxide for 1 hour.

' Example III As in Example ll, 1 mol of dipentaerythritol wasesterified with 4 mols of the Diphenolic Acid from phenol and levulinicacid and 2 mols of linseed oil fatty acids to give a product having anacid value of 6.2 and a softenammonium hydroxide, and boiling toluene,for 1 hour. This film, While being of extreme glass-like hardness, wasstill suificiently flexible to ribbon freely under a knife edge.

, Example I V This example is an exact duplication of Example 111 exceptthat the linseed acids were replaced with dehydrated castor oil acids.The product, on baking for minutes at 200 C., again gave a very hard,tack-free film which ribboned under a knife edge and withstood 10%ammonium hydroxide for 1 hour.

Example V To I mol of Chinawood oil acids heated at 225 C. was added 1.1mol pentaerythritol with continuous agitation and held at thistemperature until the acid value had reached 6. To 86 parts of thisproduct in a 3-neck flask provided with a reflux condenser attachedthrough a water trap was added 171.5 parts of the Diphenolic Acidprepared from phenol and levulinic acid, and the reaction mixture heatedwith continuous stirring to 210 C. at which point a suflicient amount ofxylene was added to give continuous reflux at the esterificationtemperature. The reaction mixture was heated with continuous agitationat 210-220 C. for a period of 1 hour and minutes, finally removing thexylene by applying a vacuum of around 30 mm. The resulting product had asoftening point of 95 C.

Example VI A mixture of 300 parts of Diphenolic Acid prepared from 2mols of mixed meta-ortho-cresol and 1 mol of levulinic acid and havingan acid value of 163, 280 parts of oleic acid and 70 parts of ethyleneglycol in a 3-neck .6 of870-1025) and 224 parts linseed oil acids in a3-neck flask equipped with a mechanical agitator and a reflux condenserattached through a water trap was heated at 220-224 C. for a period of 1/2 hours. To this mixture 57.2 parts of Diphenolic Acid was added andthe temperature maintained at 230 -240 C. for an additional 2% hours togive a hard resin having an acid value of 7 and a softening point of 63C. To 100 parts of the mixed ester and 20 parts of xylene was added 2.2parts of pformaldehyde and 2 drops of 37% aqueous hydrochloric acid, andthe resultant mixture heated with agitation at 104 C. for approximately1 hour. Ninety parts of this product was dissolved in S200 to give anonvolatile content of 50%. A thin film of this coating flowed on to asteel panel and baked for 15 minutes at 150 C. gave a hard, flexiblefihn. 1

While there are above disclosed but a limited number of embodiments ofthe product of the invention herein presented, it is possible to producestill other embodiments without departing from the inventive conceptherein disclosed, and it is desired, therefore, that only suchlimitations be imposed on the appended claims as are stated therein, orrequired by the prior art.

I claim:

1. A new composition of matter comprising a soluble and fusible mixedester of a polyhydric alcohol having a molecular weight of not more thanabout 8,000 and (1) at least one ethylenically unsaturated aliphaticmonocarboxylic acid having at least about 10 carbon atoms and (2) apentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is ahydroxyphenyl radical and is free from substituents other than alkylgroups of from 1-5 carbon atoms, the phenolic hydroxyl groups of saidpentanoic acid being substantially completely unreacted.

2. The composition of claim 1 wherein the pentanoic acid consistsessentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein thehydroxyaryl radical is a hydroxyphenyl radical and is free fromsubstituents other than alkyl groups of one carbon atom.

3. The composition of claim 1 wherein the pentanoic acid is 4,4 bis(4-hydroxyphenyl)pentanoic acid.

flask equipped with a mechanical agitator and a reflux condenserattached through a water trap was heated to 210 C. A sufficient amountof xylene was added to give refluxing at the esterification temperature.The reaction mixture was heated with continuous agitation until the acidvalue reached 10. The xylene was removed by applying a vacuum of around30 mm. The viscosity of the final product was X+ (Gardner BubbleViscosimeter) and the acid value was 10.8.

Example VII A resinous alcohol was prepared by reacting 1 molptert-butyl-phenol with 1.5 mols formaldehyde followed by reaction with1.5 mols ethylene chlorohydrin. A mixture of 89.5 parts of this alcohol,33.6 parts of linseed oil acids, and 17.2 parts of Diphenolic Acid in a3-neck flask equipped With a mechanical agitator and a reflux condenserattached through a water trap was heated to 220 C. and held at 220-260C. for a period of 3 /2 hours to give a hard brittle resin having anacid number below 5 and a softening point of 95 C.

Example VII A mixture of 278 parts of Epon 1004 (a resinous polyhydricalcohol manufactured by Shell Chemical Corporation containing someepoxide, prepared from epichlorohydrin andbis(4-hydroxyphenyl)-isopropylidene having a softening point of 95-105C. and an epoxide equivalent 4. The composition of claim 3 wherein theunsaturated monocarboxylic acid is oleic acid.

5. The composition of claim 3 wherein the unsaturated monocarboxylicacid is linseed oil acids.

6. The composition of claim 3 wherein the unsaturated monocarboxylicacid is dehydrated castor oil acids.

7. The composition of claim 3 wherein the unsaturated monocarboxylicacid is Chinawood oil acids.

8. The composition of claim 3 wherein the unsaturated monocarboxylicacid is soyabean oil acids.

9. The composition of claim 3 wherein the polyhydric alcohol isglycerol.

10. The composition of claim 3 wherein the polyhydric alcohol isethylene glycol.

11. The composition of claim 3 wherein the polyhydric alcohol ispentaerythritol.

12. The composition of claim 3 wherein the polyhydric alcohol isdipentaerythritol.

13. A new composition of matter comprising a soluble and fusible mixedester of glycerol and (1) linseed oil acids and (2) 4,4bis(4-hydroxyphenol)pentanoic acid.

14. A new composition of matter comprising a soluble and fusible mixedester of pentaerythritol and (1) linseed oil acids and (2) 4,4bis(4-hydroxyphenyl)pentanoic acid.

15. A new composition of matter comprising a soluble and fusible mixedester of dipentaerythritol and (1) linseed oil acids and (2) 4,4bis(4-hydroxyphenyl)pentanoic acid.

16. A new composition of matter comprising a soluble and fusible mixedester of dipentaerythritol and (1) dehydrated castor oil acids and (2)4,4 bis(4-hydroxyphenyl)pentanoic acid.

17. A new composition of matter comprising a soluble 'hydrin.

hand fusible mixed ester. of pentaerythritol and v l 1 China- Wood oilacids and (2) 4,34 'bis(4-hydroxyphenyl)pentanoic acid.

18. A;composition of matter comprising a solublevand fusible mixed esterof a resinou's polymeric polyhydric alcohol-having a molecular Weight ofnot more than about 8,000 and (:1) at least one ethylenicallyunsaturated-aliphatic monocarboxylic acid of at least aboutt10 carbonnoic acid being substantially completely unreacted.

19.Thei com-position of claim 18'Wherein said resinous polymericpolyhydric alcohol is a fusible ahydroxyaryl ether'of a phenol-aldehydecondensate and a monochloro- 20.'jThe composition of claim 18 whereinsaid resinous containing 1-2 epoxy groups and being free fromfunctional,groupsnotherathan hydroxyl and epoxyvgroups.

21. Anewcornposition of matter comprising a mixed ester of ,thereactionproduct of ethylene -,chlorohydrin with the condensation productof formaldehyde, and paratert-butylphenol, soyabean oil acids and 4,4bis(4-hydroXyphenyl) pentanoic acid.

.22. A method ofpreparing anew soluble andfusible composition of matterwhich comprises heating to attemperature of from l90-275 C. a mixture ofsubstantial amounts of a polyhydric alcohol having a molecular weight ofnot more than about 8,000 and (1 at least one ethylenically unsaturatedaliphatic monocarboxylic tacid havingat leastabout 10 carbon atomsandt(2) a pentanoic acid consisting essentially of 4,4bis(4-hydroxyaryl)- ,pentanoic acid whereinlthe hydroxyaryl radical'isanhydroxyphenyl radical and is free from substituentsother than alkylgroups of 1-5 carbon atoms, the phenolic hydroxyl groups of saidpentanoic acid being substantially polyhydric alcohol is apolyetherderivative of a dihydric '20 completely unreacted.

phenol and has alternating aliphatic chains and. aromatic nuclei unitedthrough ether oxygen, said resinous alcohol No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction October 6, 1959Patent No. 2,907,724

Sylvan Owen Greenlee It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionand that the said Letters Patent should read as corrected below.

Column 1, following line 52, the extreme left-hand nstead of as in thepatent:

appear as shown below i on on CH3 omomoom column 4, line 35, fordiphenolic acid read Diphen0lic Acid-- column 5, line 70, for ExampleVII read -Eacample Vlll-; column 6, line 63, for 4,4 bisl-hydroxyphenol) pentanoic acid read -43 bis(ei-hydroxyphenyl)pentanoicacid-.

Signed and sealed this 17th day of May 1960.

portion of the vformula should Attest: KARL H. AXLINE, ROBERT C. WATSON,Commissioner of Patents.

Attestz'ng Ofiicer.

1. A NEW COMPOSITION OF MATTER COMPRISING A SOLUBLE AND FUSIBLE MIXEDESTER OF A POLYHYDRIC ALCOHOL HAVING A MOLECULAR WEIGHT OF NOT MORE THANABOUT 8,000 AND (1) AT LEAST ONE ETHYLENICALLY UNSATURATGED ALIPHATICMONOCARBOXYLIC ACID HAVING AT LEAST ABOUT 10 CARBON ATOMS AND (2) APENTANIOC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4-HYDROXYPHENYL RADICALAND IS FREE FROM SUBRADICALS IS A HYDROXYPHENYL RADICALS AND IS FREEFROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS, THEPHENOLIC HYDROXYL GROUPS OF SAID PENTANOIC ACID BEING SUBSTANTIALLYCOMPLETELY UNREACTED.